TWI622619B - Composite resin composition and planar connector formed from the composite resin composition - Google Patents
Composite resin composition and planar connector formed from the composite resin composition Download PDFInfo
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Abstract
在於提供可得平面度、焊接強度及耐龜裂性優良的平面狀連結器之複合樹脂組合物及由該複合樹脂組合物成形之平面狀連結器。 It is a composite resin composition which provides a planar connector excellent in flatness, weld strength, and crack resistance, and a planar connector formed from the composite resin composition.
一種複合樹脂組合物，包含：(A)含有即定構成成分之液晶性聚合物；(B)玻璃纖維；及(C)選自由雲母及滑石所組成之群之1以上的板狀無機填充材之複合樹脂組合物，上述(A)液晶性聚合物對複合樹脂組合物全體為45~60質量%，上述(B)玻璃纖維，對複合樹脂組合物全體為超過25質量%30質量%以下，上述(C)選自由雲母及滑石所組成之群之1以上的板狀無機填充材之總量對複合樹脂組合物全體為15~20質量%。 A composite resin composition comprising: (A) a liquid crystalline polymer containing a predetermined constituent component; (B) a glass fiber; and (C) a plate-shaped inorganic filler selected from the group consisting of mica and talc; In the composite resin composition, the (A) liquid crystalline polymer is 45 to 60% by mass in total of the composite resin composition, and the (B) glass fiber is more than 25% by mass and 30% by mass or less based on the total of the composite resin composition. The total amount of the plate-like inorganic filler (C) selected from the group consisting of mica and talc is 15 to 20% by mass based on the total amount of the composite resin composition.
Description
本發明係關於複合樹脂組合物及由該複合樹脂組合物成形之平面狀連結器。 The present invention relates to a composite resin composition and a planar connector formed from the composite resin composition.
液晶性聚合物，由於流動性等優良，先前被採用作為各種電子零件的材料。 The liquid crystalline polymer has been used as a material for various electronic parts because of its excellent fluidity and the like.
特別是，隨著近幾年的電子機器的高性能化，有對具有細微構造等的電子零件(連結器等)之需求。為滿足如此之需求，例如於專利文獻1，揭示有一種平面狀連結器，其係由既定的液晶性聚合物、無機填充劑及玻璃纖維所組成之複合樹脂組合物成形，不容易在平面狀連結器的柵格部等發生破裂(亦稱為「龜裂」)，而具有耐龜裂性。 In particular, with the increase in the performance of electronic devices in recent years, there is a demand for electronic components (connectors, etc.) having fine structures and the like. In order to satisfy such a demand, for example, Patent Document 1 discloses a planar connector formed of a composite resin composition composed of a predetermined liquid crystalline polymer, an inorganic filler, and a glass fiber, which is not easily planar. Cracks (also called "cracks") occur in the grid portion of the connector, and are resistant to cracking.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2012-214652號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2012-214652
但是，難以不犧牲平面度，而穩定地得到耐龜裂 性高的平面狀連結器。此外，根據本發明者的研究的結果，發現平面狀連結器的龜裂的發生，係與該連結器的焊接強度相關。總之，為抑制發生龜裂，需要提升連結器的焊接強度。 However, it is difficult to obtain crack resistance stably without sacrificing flatness. Highly flat connector. Further, according to the results of the study by the inventors, it was found that the occurrence of cracks in the planar connector is related to the welding strength of the connector. In short, in order to suppress the occurrence of cracks, it is necessary to increase the welding strength of the connector.
本發明，係有鑑於該情形而完成者，以提供可得平面度、焊接強度及耐龜裂性優良的平面狀連結器的複合樹脂組合物及由該複合樹脂組合物成形之平面狀連結器為目標。 The present invention provides a composite resin composition having a planar connector excellent in flatness, weld strength, and crack resistance, and a planar connector formed from the composite resin composition. For the goal.
本發明者們，發現藉由組合包含既定量特定的構成單位的液晶性聚合物、玻璃纖維及既定的板狀無機填充材，可解決上述課題。具體而言，本發明可提供如下者。 The present inventors have found that the above problems can be solved by combining a liquid crystalline polymer containing a specific constituent unit, a glass fiber, and a predetermined plate-shaped inorganic filler. Specifically, the present invention can provide the following.
(1)一種複合樹脂組合物，包含：(A)液晶性聚合物；(B)玻璃纖維；及(C)選自由雲母及滑石所組成之群之1以上的板狀無機填充材之複合樹脂組合物，上述(A)液晶性聚合物，作為必要的構成成分，包含下述構成單位：(I)4-羥基安息香酸；(II)2-羥基-6-萘甲酸；(III)對苯二甲酸；(IV)間苯二甲酸；及(V)4,4'-二羥基聯苯，(I)的構成單位對全構成單位為35~75莫耳%，(II)的構成單位對全構成單位為2~8莫耳%，(III)的構成單位對全構成單位為4.5~30.5莫耳%，(IV)的構成單位對全構成單位為2~8莫耳%，(V)的構成單位對全構成單位為12.5~32.5莫耳%，(II)及(IV)的構成單位的總量對全構成單位為4~10莫耳%，上述(A)液晶性聚合物對複合樹脂組合物全體為45~60質 量%，上述(B)玻璃纖維對複合樹脂組合物全體超過25質量%30質量%以下，上述(C)選自由雲母及滑石所組成之群之1以上的板狀無機填充材對複合樹脂組合物全體總量為15~20質量%。 (1) A composite resin composition comprising: (A) a liquid crystalline polymer; (B) a glass fiber; and (C) a composite resin of a plate-like inorganic filler selected from the group consisting of mica and talc; The composition (A) liquid crystalline polymer, as an essential constituent component, comprises the following constituent units: (I) 4-hydroxybenzoic acid; (II) 2-hydroxy-6-naphthoic acid; (III) p-benzoic acid (IV) isophthalic acid; and (V) 4,4'-dihydroxybiphenyl, the constituent unit of (I) is 35 to 75 mol% of the total constituent unit, and the constituent unit of (II) The total constituent unit is 2 to 8 mol%, the constituent unit of (III) is 4.5 to 30.5 mol% for the total constituent unit, and the constituent unit of (IV) is 2 to 8 mol% for the total constituent unit, (V) The constituent unit is 12.5 to 32.5 mol% for the total constituent unit, and the total amount of the constituent units of (II) and (IV) is 4 to 10 mol% for the total constituent unit, and the above (A) liquid crystalline polymer is compounded. The resin composition is 45~60 The amount of the above-mentioned (B) glass fiber to the composite resin composition is more than 25% by mass and 30% by mass or less, and the above (C) is selected from the group consisting of mica and talc, and the plate-like inorganic filler is combined with the composite resin. The total amount of the objects is 15 to 20% by mass.
(2)一種平面狀連結器，由(1)所記載的複合樹脂組合物成形，於外框部的內部具有柵格構造，於上述柵格構造的柵格部的間距間隔為1.5mm以下。 (2) A planar connector formed of the composite resin composition according to (1), having a lattice structure inside the outer frame portion, and a pitch interval of the grating portion of the grating structure of 1.5 mm or less.
根據本發明，可提供可得平面度、焊接強度及耐龜裂性優良的平面狀連結器之複合樹脂組合物，以及由該複合樹脂組合物成形之平面狀連結器。 According to the present invention, it is possible to provide a composite resin composition of a planar connector excellent in flatness, weld strength and crack resistance, and a planar connector formed from the composite resin composition.
第1圖係於實施例成形之平面狀連結器之圖。(a)係平面狀連結器之平面圖。(b)係(a)中的A部之詳細情形。再者，圖中的數值單位為mm。 Fig. 1 is a view showing a planar connector formed in the embodiment. (a) is a plan view of a planar connector. (b) The details of Part A in (a). Furthermore, the numerical unit in the figure is mm.
以下，具體說明關於本發明之實施形態。再者，本發明並非限定於以下的實施形態。 Hereinafter, embodiments of the present invention will be specifically described. Furthermore, the present invention is not limited to the following embodiments.
[複合樹脂組合物] [Composite resin composition]
本發明之複合樹脂組合物，各包含既定量的特定液晶性聚合物、玻璃纖維、及板狀無機填充材。以下，說明關於構成本 發明之複合樹脂組合物之成分。 The composite resin composition of the present invention each contains a specific amount of a specific liquid crystalline polymer, a glass fiber, and a plate-like inorganic filler. Hereinafter, the description about the constitution A component of the composite resin composition of the invention.
(液晶性聚合物) (liquid crystalline polymer)
在於本發明之液晶性聚合物，作為必要構成成分，包含下述構成單位：(I)4-羥基安息香酸(亦稱為「HBA」)、(II)2-羥基-6-萘甲酸(亦稱為「HNA」)、(III)對苯二甲酸(亦稱為「TA」)、(IV)間苯二甲酸(亦稱為「IA」)及(V)4,4'-二羥基聯苯(亦稱為「BP」)。 The liquid crystalline polymer of the present invention contains, as essential constituents, the following constituent units: (I) 4-hydroxybenzoic acid (also referred to as "HBA"), and (II) 2-hydroxy-6-naphthoic acid (also Known as "HNA"), (III) terephthalic acid (also known as "TA"), (IV) isophthalic acid (also known as "IA") and (V) 4,4'-dihydroxyl Benzene (also known as "BP").
在於本發明之液晶性聚合物，將上述的構成單位以特定比例包含。即，(I)的構成單位對全構成單位為35~75莫耳%(以40~65莫耳%為佳)。(II)的構成單位對全構成單位為2~8莫耳%(以3~7莫耳%為佳)。(III)的構成單位對全構成單位為4.5~30.5莫耳%(以13~26莫耳%為佳)。(IV)的構成單位對全構成單位為2~8莫耳%(以3~7莫耳%為佳)。(V)的構成單位對全構成單位為12.5~32.5莫耳%(以15.5~29莫耳%為佳)。(II)及(IV)的構成單位的總量對全構成單位為4~10莫耳%(以5~10莫耳%為佳)。 In the liquid crystalline polymer of the present invention, the above-mentioned constituent units are contained in a specific ratio. That is, the constituent unit of (I) is 35 to 75 mol% (more preferably 40 to 65 mol%) for the total constituent unit. The constituent unit of (II) is 2 to 8 mol% (more preferably 3 to 7 mol%) for the total constituent unit. The constituent unit of (III) is 4.5 to 30.5 mol% for the total constituent unit (preferably 13 to 26 mol%). The constituent unit of (IV) is 2 to 8 mol% (more preferably 3 to 7 mol%) for the total constituent unit. The constituent unit of (V) is 12.5 to 32.5 mol% for the total constituent unit (preferably 15.5 to 29 mol%). The total amount of the constituent units of (II) and (IV) is 4 to 10 mol% for the total constituent unit (preferably 5 to 10 mol%).
(I)的構成單位對全構成單位未滿35莫耳%或超過75莫耳%，則液晶性聚合物的熔點會顯著地變高，製造平面狀連結器等的成形品時，液晶性聚合物在反應器內固化，而有無法製造所期望分子量之液晶性聚合物的可能性而不佳。 When the constituent unit of (I) is less than 35 mol% or more than 75 mol% of the total constituent unit, the melting point of the liquid crystalline polymer is remarkably high, and when a molded article such as a flat connector is produced, liquid crystal polymerization is carried out. The solidification of the material in the reactor is not preferable because it is impossible to produce a liquid crystalline polymer having a desired molecular weight.
(II)的構成單位對全構成單位未滿2莫耳%，則於製造平面狀連結器等的成形品時，有於柵格部等發生龜裂的可能性而不佳。此外，(II)的構成單位對全構成單位超過8莫耳%，則液晶性聚合物的耐熱性變低而不佳。 When the constituent unit of (II) is less than 2 mol% of the total constituent unit, when a molded article such as a flat connector is manufactured, there is a possibility that cracking occurs in the grid portion or the like. Further, when the constituent unit of (II) exceeds 8 mol% of the total constituent unit, the heat resistance of the liquid crystalline polymer is lowered.
(III)的構成單位對全構成單位未滿4.5莫耳%或超過30.5莫耳%，則液晶性聚合物的熔點會顯著地變高，製造平面狀連結器等的成形品時，液晶性聚合物在反應器內固化，而有無法製造所期望分子量之液晶性聚合物的可能性而不佳。 When the constituent unit of (III) is less than 4.5 mol% or more than 30.5 mol% of the total constituent unit, the melting point of the liquid crystalline polymer is remarkably high, and when a molded article such as a flat connector is produced, liquid crystal polymerization is carried out. The solidification of the material in the reactor is not preferable because it is impossible to produce a liquid crystalline polymer having a desired molecular weight.
(IV)的構成單位對全構成單位未滿2莫耳%，則製造平面狀連結器等的成形品時，有於柵格部等發生龜裂的可能性而不佳。此外，(IV)的構成單位對全構成單位超過8莫耳%，則液晶性聚合物的耐熱性變低而不佳。 When the constituent unit of (IV) is less than 2 mol% of the total constituent unit, when a molded article such as a planar fastener is produced, there is a possibility that cracking occurs in the grid portion or the like. Further, when the constituent unit of (IV) exceeds 8 mol% of the total constituent unit, the heat resistance of the liquid crystalline polymer is lowered.
(V)的構成單位對全構成單位未滿12.5莫耳%或超過32.5莫耳%，則液晶性聚合物的熔點會顯著地變高，製造平面狀連結器等的成形品時，液晶性聚合物在反應器內固化，而有無法製造所期望分子量之液晶性聚合物的可能性而不佳。 When the constituent unit of (V) is less than 12.5 mol% or more than 32.5 mol% of the total constituent unit, the melting point of the liquid crystalline polymer is remarkably high, and when a molded article such as a flat connector is produced, liquid crystal polymerization is carried out. The solidification of the material in the reactor is not preferable because it is impossible to produce a liquid crystalline polymer having a desired molecular weight.
(II)及(IV)的構成單位的總量對全構成單位未滿4莫耳%，則液晶性聚合物的結晶化熱可能變得2.5J/g以上。此時，於製造平面狀連結器等的成形品時，有於柵格部等發生龜裂的可能性而不佳。液晶性聚合物的結晶化熱較佳的值為2.3J/g以下，以2.0J/g以下更佳。再者，結晶化熱係表示液晶性聚合物的結晶化狀態，係藉由示差熱量測定所求得之值。具體而言，將液晶性聚合物由室溫20℃/分的升溫條件測定時，所觀測之吸熱波峰溫度(Tm1)之觀測後，以Tm1+40℃的溫度保持2分鐘之後，以20℃/分的降溫條件測定時所觀測之發熱波峰溫度之波峰所求得之發熱波峰的熱量。 When the total amount of the constituent units of (II) and (IV) is less than 4 mol% of the total constituent unit, the heat of crystallization of the liquid crystalline polymer may become 2.5 J/g or more. At this time, when a molded article such as a planar connector is manufactured, there is a possibility that cracks may occur in the grating portion or the like. The crystallization heat of the liquid crystalline polymer is preferably 2.3 J/g or less, more preferably 2.0 J/g or less. In addition, the crystallization heat is a crystallization state of the liquid crystalline polymer, and is a value obtained by differential calorimetry measurement. Specifically, when the liquid crystalline polymer was measured at a temperature rise condition of room temperature of 20 ° C /min, the observed endothermic peak temperature (Tm1) was observed, and the temperature was maintained at Tm1 + 40 ° C for 2 minutes, and then at 20 ° C. The heat of the heat generation peak obtained by the peak of the heat peak temperature observed during the measurement of the temperature drop condition.
此外，(II)及(IV)的構成單位的總量對全構成單位超過10莫耳%，則液晶性聚合物的耐熱性變低而不佳。 Further, when the total amount of the constituent units of (II) and (IV) exceeds 10 mol% of the total constituent unit, the heat resistance of the liquid crystalline polymer is lowered.
再者，在於本發明之液晶性聚合物，在不阻礙本發明之目的的範圍導入習知之其他構成單位。 Further, the liquid crystalline polymer of the present invention is introduced into other conventional constituent units within a range not inhibiting the object of the present invention.
在於本發明之液晶性聚合物，可藉由將上述構成單位，以直接聚合法、酯交換法、熔融聚合法、溶液聚合法、漿料聚合法、固相聚合法等聚合而得。 The liquid crystalline polymer of the present invention can be obtained by polymerization of the above constituent units by a direct polymerization method, a transesterification method, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like.
在於上述構成單位的聚合，加上上述構成單位，可並用對上述構成單位作為醯化劑、或酸氯化物衍生物，將末端活化之單體。醯化劑，可舉醋酸酐等的酸酐等。 In the polymerization of the above-mentioned constituent unit, the above-mentioned constituent unit may be used in combination with the above-mentioned constituent unit as a deuteration agent or an acid chloride derivative to activate the terminal. The oxime agent may, for example, be an acid anhydride such as acetic anhydride.
在於上述構成單位的聚合，可使用各種觸媒，可舉例如二烷基錫氧化物、二芳基錫氧化物、二氧化鈦、烷氧基鈦矽酸鹽類、烷氧基鈦酸酯類、羧酸的鹼金屬鹽類、鹼土類金屬鹽類、路易斯酸鹽(BF3等)等。觸媒的使用量，對上述構成單位的總量約為0.001~1質量%，以約0.003~0.2質量%為佳。 In the polymerization of the above constituent units, various catalysts can be used, and examples thereof include a dialkyl tin oxide, a diaryl tin oxide, a titanium oxide, an alkoxy titanium niobate, an alkoxy titanate, and a carboxyl group. An alkali metal salt of an acid, an alkaline earth metal salt, a Lewis acid salt (such as BF 3 or the like). The total amount of the catalyst used is about 0.001 to 1% by mass, and preferably about 0.003 to 0.2% by mass.
聚合反應的條件，只要是可進行上述構成單位的聚合進的條件，並無特別限定，例如，可為反應溫度200~380℃，最終到達壓力0.1~760Torr(即，13~101,080Pa)。 The conditions of the polymerization reaction are not particularly limited as long as the polymerization can be carried out in the above-mentioned constituent units. For example, the reaction temperature is 200 to 380 ° C, and the final pressure is 0.1 to 760 Torr (that is, 13 to 101,080 Pa).
聚合反應，可係將全原料單體、醯化劑及觸媒放入同一反應容器開始反應的方法(一段模式)，亦可係將原料單體(I)、(II)及(V)的羥基藉由醯化劑醯化之後，與(III)及(IV)的羧基反應的方法(二段模式)。 The polymerization reaction may be a method in which the whole raw material monomer, the oximation agent and the catalyst are put into the same reaction vessel to start the reaction (a mode), or the raw material monomers (I), (II) and (V) A method of reacting a hydroxyl group with a carboxyl group of (III) and (IV) after deuteration of a hydroxyl group (two-stage mode).
由上述構成單位(I)或(V)所得之液晶性聚合物，根據構成成分及液晶性聚合物中順序分佈，雖亦存在有不形成異向性熔融相者，惟兼具熱穩定性及易加工性之點，在於本發明之液晶性聚合物，以可形成異向性熔融相者，即，熔融時顯示 光學異向性之液晶性聚合物為佳。 The liquid crystalline polymer obtained by the above-mentioned structural unit (I) or (V) has a thermal distribution stability even if it does not form an anisotropic melt phase depending on the constituent components and the liquid crystal polymer. The point of easy processability lies in the liquid crystalline polymer of the present invention, which can form an anisotropic melt phase, that is, display when molten An optically anisotropic liquid crystalline polymer is preferred.
熔融異向性的性質，可藉由利用直交偏光片的慣用偏光檢查方法確認。具體而言，熔融異向性，係使用偏光顯微鏡(奧林巴斯(股)製等)，將載置於加熱台(Linkam公司製等)的試料熔融，於氮氣氛下以150倍的倍率觀察確認。熔融時顯示光學異向性的液晶性聚合物，係光學性異向性，插入正交偏光片之間時可使光透過。試料為光學性異向性，則例如即使在熔融靜止液狀態，可使偏光穿透。 The nature of the melting anisotropy can be confirmed by a conventional polarizing inspection method using an orthogonal polarizer. Specifically, the melting anisotropy is melted by a polarizing microscope (manufactured by Olympus Co., Ltd.), and the sample placed on a heating stage (manufactured by Linkam Co., Ltd.) is melted at a magnification of 150 times in a nitrogen atmosphere. Observe and confirm. The liquid crystalline polymer exhibiting optical anisotropy at the time of melting is optically anisotropic, and transmits light when inserted between the orthogonal polarizers. When the sample is optically anisotropic, for example, even in the state of melting the stationary liquid, the polarized light can be penetrated.
再者，以較熔點高10~40℃的溫度，在於剪速度1000/秒的液晶性聚合物的熔融黏度，以1×105Pa．s以下(進一步以5Pa．s以上且1×102Pa．s以下為佳)，在於平面狀連結器的柵格部的成形時，可確保複合樹脂組合物的流動性，不使填充壓力過度之點而佳。 Furthermore, the temperature at which the melting point is 10 to 40 ° C is higher than the melting viscosity of the liquid crystalline polymer having a shear rate of 1000 / sec, at 1 × 10 5 Pa. s or less (more preferably 5 Pa.s or more and 1 × 10 2 Pa.s or less), in the molding of the grid portion of the planar connector, the fluidity of the composite resin composition can be ensured, and the filling pressure is not excessive. The point is better.
本發明之複合樹脂組合物，係將上述液晶性聚合物，於複合樹脂組合物中，對複合樹脂組合物全體包含45~60質量%。液晶性聚合物的量，對複合樹脂組合物全體未滿45質量%，則流動性會惡化而不佳。液晶性聚合物的量，對複合樹脂組合物全體超過60質量%，則由複合樹脂組合物所得之平面狀連結器等的成形品的彎曲彈性模數及耐龜裂性會下降而不佳。本發明之複合樹脂組合物，係將上述液晶性聚合物，於複合樹脂組合物中，對複合樹脂組合物全體包含50~60質量%為佳。 In the composite resin composition of the present invention, the liquid crystalline polymer is contained in the composite resin composition in an amount of 45 to 60% by mass based on the entire composite resin composition. When the amount of the liquid crystalline polymer is less than 45% by mass based on the total amount of the composite resin composition, the fluidity may be deteriorated. When the amount of the liquid crystalline polymer is more than 60% by mass in the total amount of the composite resin composition, the molded product such as a planar fastener obtained from the composite resin composition may have a poor bending elastic modulus and crack resistance. In the composite resin composition of the present invention, the liquid crystalline polymer is preferably contained in the composite resin composition in an amount of 50 to 60% by mass based on the entire composite resin composition.
(玻璃纖維) (glass fiber)
本發明之複合樹脂組合物，係於複合樹脂組合物中，對複 合樹脂組合物全體包含超過25質量%30質量%以下的玻璃纖維。 The composite resin composition of the present invention is in a composite resin composition, and is complex The entire resin composition contains more than 25% by mass and 30% by mass or less of glass fibers.
玻璃纖維的量，對複合樹脂組合物全體在25質量%以下，則由複合樹脂組合物所得之成形品的焊接強度低，而成形品為平面狀連結器時，容易在其柵格部等發生龜裂。 When the amount of the glass fiber is 25% by mass or less based on the total amount of the composite resin composition, the molded article obtained from the composite resin composition has a low welding strength, and when the molded article is a flat connector, it is likely to occur in the grid portion or the like. Cracked.
玻璃纖維的量，對複合樹脂組合物全體超過30質量%，則不僅組合物的流動性會惡化，且對複合樹脂組合物全體包含超過30質量%的玻璃纖維的複合樹脂組合物所得之平面狀連結器，平面度差，而可能會扭曲。 When the amount of the glass fiber is more than 30% by mass in the total amount of the composite resin composition, the fluidity of the composition is deteriorated, and the composite resin composition containing more than 30% by mass of the glass fiber in the entire composite resin composition has a planar shape. The connector is flat and may be distorted.
本發明者的研究的結果，發現成形品(平面狀連結器等)之焊接強度，與該成形品的龜裂數之間有所相關。具體而言，使用各種複合樹脂組合物，關於以下述實施例所記載的方法所得之平面狀連結器及試驗片，以下述實施例所記載的測定條件，研究焊接強度及龜裂數。結果，由玻璃纖維的量，係對複合樹脂組合物全體為25質量%以下的複合樹脂組合物所得之試驗片的焊接強度為10kgf以下(根據情形為8kgf以下)，且，在由同複合樹脂組合物所得之平面狀連結器確認到多數龜裂。另一方面，由對複合樹脂組合物全體包含超過25質量%30質量%以下(27.5~30質量%)的玻璃纖維的複合樹脂組合物所得之試驗片之焊接強度超過10kgf，且，由同複合樹脂組合物所得之平面狀連結器幾乎沒有發現龜裂。 As a result of the study by the inventors, it was found that the welding strength of the molded article (planar connector or the like) is related to the number of cracks of the molded article. Specifically, the various types of composite resin compositions were used, and the planar connectors and test pieces obtained by the methods described in the following examples were used to examine the welding strength and the number of cracks under the measurement conditions described in the following examples. As a result, the test piece obtained by the composite resin composition in which the total amount of the glass fiber is 25% by mass or less based on the total amount of the glass fiber is 10 kgf or less (in some cases, 8 kgf or less), and in the same composite resin. The planar connector obtained from the composition confirmed most cracks. On the other hand, the test piece obtained from the composite resin composition containing the glass fiber of more than 25% by mass and 30% by mass or less (27.5 to 30% by mass) of the entire composite resin composition has a weld strength of more than 10 kgf, and is compounded by the same compound. No crack was found in the planar connector obtained from the resin composition.
在於本發明之玻璃纖維的平均纖維長，並無特別限定，以250~800μm為佳。平均纖維長未滿250μm，則由複合樹脂組合物所得之平面狀連結器等的成形品的柵格部等有發 生龜裂的可能性而不佳。平均纖維長超過800μm，則流動性惡化，而複合樹脂組合物有難以成形的可能性而不佳。 The average fiber length of the glass fiber of the present invention is not particularly limited, and is preferably 250 to 800 μm. When the average fiber length is less than 250 μm, the grid portion of the molded article such as a planar connector obtained from the composite resin composition is emitted. The possibility of cracking is not good. When the average fiber length exceeds 800 μm, the fluidity deteriorates, and the composite resin composition may be difficult to form.
此外，在於本發明之玻璃纖維的纖維徑，並無特別限制，一般使用5~15μm程度者。 Further, the fiber diameter of the glass fiber of the present invention is not particularly limited, but generally 5 to 15 μm is used.
(板狀無機填充材) (plate-shaped inorganic filler)
本發明之複合樹脂組合物，包含選自由雲母及滑石所組成之群之1以上板狀無機填充材。藉由將該板狀無機填充材與玻璃纖維一起包含於複合樹脂組合物，可不使複合樹脂組合物的流動性惡化，而可得可成形平面度、耐龜裂性及焊接強度優良的成形體的複合樹脂組合物。 The composite resin composition of the present invention comprises a plate-shaped inorganic filler selected from the group consisting of mica and talc. By including the plate-like inorganic filler and the glass fiber in the composite resin composition, it is possible to obtain a molded body excellent in moldability, crack resistance, and weld strength without deteriorating the fluidity of the composite resin composition. Composite resin composition.
包含於本發明之複合樹脂組合物中的板狀無機填充材的總量，對複合樹脂組合物全體為15~20質量%。板狀無機填充材以該範圍包含於複合樹脂組合物中，則可補強藉由玻璃纖維所發揮的成形體的焊接強度的提升效果及減少龜裂數的效果。如此得補強效果，在本發明的複合樹脂組合物中的玻璃纖維的量接近上限(即，對複合樹脂組合物全體為30質量%)之值時可顯著地發揮。 The total amount of the plate-like inorganic filler contained in the composite resin composition of the present invention is 15 to 20% by mass based on the total amount of the composite resin composition. When the plate-like inorganic filler is contained in the composite resin composition in this range, the effect of improving the weld strength of the molded body by the glass fiber and the effect of reducing the number of cracks can be enhanced. When the amount of the glass fiber in the composite resin composition of the present invention is close to the upper limit (that is, 30% by mass of the entire composite resin composition), the reinforcing effect can be remarkably exhibited.
〔雲母〕 [mica]
雲母係包含鋁、鉀、鎂、鈉、鐵等的矽酸鹽礦物的粉碎物。在於本發明之雲母，可舉白雲母、金雲母、黑雲母、人造雲母等，該等之中，由色相良好，低價格之點，以白雲母為佳。 Mica is a pulverized product of a citrate mineral such as aluminum, potassium, magnesium, sodium or iron. The mica of the present invention may be muscovite, phlogopite, biotite, or artificial mica. Among them, muscovite is preferred because of good hue and low price.
此外，在於雲母的製造，粉碎礦物的方法，已知有濕式粉碎法及乾式粉碎法。濕式粉碎法，係將雲母原石以乾式粉碎機粗粉碎之後，加水做成漿料狀態，以濕式粉碎作本粉 碎，之後進行脫水，乾燥的方法。與濕式粉碎法相比，乾式粉碎法是低成本的一般方法，惟難以將礦物粉碎的薄且細小。由可得後述之較佳的平均粒徑及濃度的雲母的理由，於本發明使用薄且細小的粉碎物為佳。因此，在於本發明，使用以濕式粉碎法製造的雲母為佳。 Further, in the production of mica and the method of pulverizing minerals, a wet pulverization method and a dry pulverization method are known. In the wet pulverization method, the mica raw stone is coarsely pulverized by a dry pulverizer, and then water is added to form a slurry state, and the powder is wet pulverized. Crushed, followed by dehydration and drying. Compared with the wet pulverization method, the dry pulverization method is a general method of low cost, but it is difficult to pulverize the mineral thin and fine. It is preferable to use a thin and fine pulverized material in the present invention from the reason that mica having a preferable average particle diameter and concentration described later can be obtained. Therefore, in the present invention, mica produced by a wet pulverization method is preferably used.
此外，在於濕式粉碎法，由於需要將被粉碎物分散於水的步驟，故為提高被粉碎物的分散效率，一般於粉碎物加入凝聚沈降劑及/或沈降助劑。凝聚沈降劑及沈降助劑，可舉聚氯化鋁、硫酸鋁、硫酸鐵、硫酸亞鐵、氯化亞銅、聚硫酸鐵、聚氯亞鐵、鐵-二氧化矽無機高分子凝聚劑、氯化亞鐵-二氧化矽無機高分子凝聚劑、熟石灰(Ca(OH)2)、苛性鈉(NaOH)、蘇打灰(Na2CO3)等。但是，該等凝聚沈降劑及沈降助劑，pH為鹼性或酸性。因此，在於本發明，使用以凝聚沈降劑及/或沈降助劑處理的雲母，則由於有引起複合樹脂組合物中的聚合物的分解，產生大量的氣體或降低聚合物的分子量等的可能性，故可能對所得成形品的性能造成不良影響。因此，使用於本發明之雲母，以濕式粉碎時，以沒有使用凝聚沈降劑及/或沈降助劑者為佳。 Further, in the wet pulverization method, since it is necessary to disperse the pulverized material in water, in order to improve the dispersion efficiency of the pulverized material, a coagulation sedimentation agent and/or a sedimentation aid are generally added to the pulverized material. Coagulation sedimentation agent and sedimentation aid, which may be polyaluminum chloride, aluminum sulfate, iron sulfate, ferrous sulfate, cuprous chloride, polyferric sulfate, polychloroferric, iron-cerium oxide inorganic polymer coagulant, Ferrous chloride-cerium oxide inorganic polymer coagulant, slaked lime (Ca(OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ), and the like. However, these coagulation sedimentation agents and precipitation aids have a pH which is alkaline or acidic. Therefore, in the present invention, mica treated with a coagulating settling agent and/or a settling aid is used, which may cause a large amount of gas or a decrease in the molecular weight of the polymer due to decomposition of the polymer in the composite resin composition. Therefore, it may adversely affect the performance of the obtained molded article. Therefore, the mica used in the present invention is preferably used in the case of wet pulverization without using a coagulating settling agent and/or a settling aid.
在於本發明之雲母，藉由微軌跡雷射繞射法測定之平均粒徑為10~100μm者為佳，以平均粒徑20~80μm者特別佳。雲母的平均粒徑未滿10μm，則由於成形品的剛性有不充分的可能性而不佳。雲母的平均粒徑超過100μm，則由於成形品的剛性及焊接強度有不充分的可能性而不佳。此外，雲母的平均粒徑超過100μm，則複合樹脂組合物的流動性有不充分的 可能性。 In the mica of the present invention, the average particle diameter measured by the micro-track laser diffraction method is preferably 10 to 100 μm, and the average particle diameter is preferably 20 to 80 μm. When the average particle diameter of mica is less than 10 μm, the rigidity of the molded article may be insufficient. When the average particle diameter of mica exceeds 100 μm, the rigidity and weld strength of the molded article may be insufficient. Further, when the average particle diameter of mica exceeds 100 μm, the fluidity of the composite resin composition is insufficient. possibility.
在於本發明之雲母的厚度，以電子顯微鏡的觀察實測的厚度，以0.01~1μm為佳，以0.03~0.3μm的特別佳。雲母的厚度未滿0.01μm，則於複合樹脂組合物的熔融加工時雲母會變得容易破裂而不佳。雲母的厚度超過1μm，則成形品的剛性有不充分的可能性。 The thickness of the mica of the present invention is preferably 0.01 to 1 μm, and particularly preferably 0.03 to 0.3 μm, as measured by an electron microscope. When the thickness of the mica is less than 0.01 μm, the mica may be easily broken at the time of melt processing of the composite resin composition. When the thickness of the mica exceeds 1 μm, the rigidity of the molded article may be insufficient.
在於本發明之雲母，亦可以矽烷偶合劑等表面處理，且/或，亦可以結合劑造粒成顆粒狀。 The mica of the present invention may be surface-treated with a decane coupling agent or the like, and/or may be granulated into a granule by a binder.
〔滑石〕 〔talc〕
在於本發明之滑石，對該滑石的全固形分量為Fe2O3、Al2O3及CaO的合計含量為2.5質量%以下，以Fe2O3及Al2O3的合計含量超過1.0質量%2.0質量%以下，且CaO的含量未滿0.5質量%者為佳。即，在於本發明之滑石，其主要成分之SiO2及MgO之外，至少包含Fe2O3、Al2O3及CaO之至少1種，可在上述範圍內包含各成分。 In the talc of the present invention, the total solid content of the talc is 2.5% by mass or less based on the total content of Fe 2 O 3 , Al 2 O 3 and CaO, and the total content of Fe 2 O 3 and Al 2 O 3 is more than 1.0 mass. It is preferably 2.0% by mass or less and the content of CaO is less than 0.5% by mass. In other words, the talc of the present invention contains at least one of Fe 2 O 3 , Al 2 O 3 and CaO in addition to SiO 2 and MgO as main components, and may contain each component within the above range.
在於上述滑石，Fe2O3、Al2O3及CaO的總量超過2.5質量%，則複合樹脂組合物的成形加工性及由該複合樹脂組合物成形之成形品的耐熱性有惡化的可能性。因此，Fe2O3、Al2O3及CaO的總量，以1.0質量%以上2.0質量%以下為佳。 When the total amount of Fe 2 O 3 , Al 2 O 3 and CaO exceeds 2.5% by mass, the molding processability of the composite resin composition and the heat resistance of the molded article formed from the composite resin composition may deteriorate. Sex. Therefore, the total amount of Fe 2 O 3 , Al 2 O 3 and CaO is preferably 1.0% by mass or more and 2.0% by mass or less.
在於本發明之滑石，以雷射繞射法測定之質量基準或體積基準的累積平均粒子徑(D50)，維持複合樹脂組合物的流動性等的觀點，以4.0~20.0μm為佳，以10~18μm更佳。 In the talc of the present invention, the cumulative average particle diameter (D 50 ) of the mass basis or the volume basis measured by the laser diffraction method is maintained at 4.0 to 20.0 μm, and the viewpoint is to maintain the fluidity of the composite resin composition. 10~18μm is better.
(其他的成分) (other ingredients)
於本發明的複合樹脂組合物，於上述成分之外，亦可調合 成核劑、碳黑、顏料、氧化防止劑、穩定劑、可塑劑、潤滑劑、脫模劑或難燃劑等。該等成分的調合量及種類，可按照所欲獲得之效果適宜調整。 The composite resin composition of the present invention may be blended in addition to the above components. Nucleating agent, carbon black, pigment, oxidation inhibitor, stabilizer, plasticizer, lubricant, mold release agent or flame retardant. The blending amount and type of the components can be appropriately adjusted according to the desired effect.
(複合樹脂組合物之製造方法) (Manufacturing method of composite resin composition)
本發明之複合樹脂組合物之製造方法，只要可將上述液晶性聚合物，與玻璃纖維等均勻混合，無特別限定，可由先前習知之樹脂組合物之製造方法適宜選擇。例如，使用單軸或雙軸擠出機等的熔融混練裝置，將各成分熔融混練擠出之後，將所得複合樹脂組合物加工為粉末、薄片、膠粒等的所期望的形態的方法。 The method for producing the composite resin composition of the present invention is not particularly limited as long as the liquid crystalline polymer can be uniformly mixed with glass fibers or the like, and can be suitably selected from the conventional methods for producing a resin composition. For example, a method in which the obtained composite resin composition is processed into a desired form such as a powder, a sheet, or a colloidal particle by melt-kneading each component using a melt kneading device such as a uniaxial or twin-screw extruder.
本發明之複合樹脂組合物，由於流動性優良，成形時的最小填充壓力不容易變得過度，可良好地成形具有如平面狀連結器的柵格部等的複雜的形狀的部分。最小填充壓力，係以成形複合樹脂組合物時，在於365℃可得良好的成形品的最小射出填充壓所特定。 In the composite resin composition of the present invention, since the fluidity is excellent, the minimum filling pressure at the time of molding is not easily excessive, and a portion having a complicated shape such as a lattice portion of a planar connector can be favorably formed. The minimum filling pressure is specified by the minimum injection filling pressure of a molded article which is excellent at 365 ° C when the composite resin composition is molded.
[平面狀連結器] [flat connector]
藉由將本發明之複合樹脂組合物成形，可得本發明之平面狀連結器。平面狀連結器的形狀，並無特別限定，可為在於外框部的內部具有柵格構造，在於該柵格構造之柵格部的間距間隔為1.5mm以下之平面狀連結器。此外，在於保持平面狀連結器的接頭的柵格部的樹脂部的寬度為0.5mm以下，產品全體的高度為5.0mm以下的非常薄壁的平面狀連結器。本發明之平面狀連結器的具體形狀，可舉例如，如第1圖所示者。 The planar connector of the present invention can be obtained by molding the composite resin composition of the present invention. The shape of the planar connector is not particularly limited, and may be a planar connector in which the inside of the outer frame portion has a lattice structure, and the lattice portion of the lattice structure has a pitch of 1.5 mm or less. In addition, it is a very thin-walled planar connector in which the width of the resin portion of the grid portion of the joint of the planar connector is 0.5 mm or less, and the height of the entire product is 5.0 mm or less. The specific shape of the planar connector of the present invention may be, for example, as shown in Fig. 1.
在於本發明之平面狀連結器的柵格部，針插入孔的形狀，並無特別限定，可為方形、圓形，異形孔。 In the grid portion of the planar connector of the present invention, the shape of the needle insertion hole is not particularly limited, and may be a square, a circular, or a special-shaped hole.
用於得到本發明的平面狀連結器的成形方法，並-無特別限定，由防止所得平面狀連結器的變形，得到具有良好的平面度的平面狀連結器，選擇殘留內部應力少的成形條件為佳。為使填充壓力低，降低所得平面狀連結器的殘留內部應力，成形機的料管溫度，以液晶性聚合物的熔點以上的溫度為佳。 The molding method for obtaining the planar connector of the present invention is not particularly limited, and a planar connector having a good flatness is obtained by preventing deformation of the obtained planar connector, and molding conditions in which residual internal stress is small are selected. It is better. In order to lower the filling pressure, the residual internal stress of the obtained planar connector is lowered, and the temperature of the tube of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystalline polymer.
此外，金屬模具溫度以70~100℃為佳。金屬模具溫度低，則有引起填充於有金屬模具之複合樹脂組合物之流動不良的可能性而不佳。金屬模具溫度高，則有發生毛邊等的問題的可能性而不佳。關於射出速度，以150mm/秒以上成形為佳。射出速度低，則有僅可得未填充成形品的可能性，即使得到完全填充的成形品，填充壓力高而成為殘留內部應力大的成形品，而有只能得到平面度差的連結器的可能性。 In addition, the temperature of the metal mold is preferably 70 to 100 ° C. When the temperature of the metal mold is low, there is a possibility that the flow of the composite resin composition filled in the metal mold is poor. When the temperature of the metal mold is high, there is a possibility that problems such as burrs occur. Regarding the injection speed, it is preferable to form it at 150 mm/sec or more. When the injection speed is low, there is a possibility that only the unfilled product can be obtained, and even if the molded article is completely filled, the filling pressure is high and the molded product having a large internal stress remains, and the connector having only a flatness difference can be obtained. possibility.
此外，本發明的平面狀連結器，係抑制變形或彎曲，平面度優良。連結器的平面度，係將連結器靜置於水平的桌上，將平面狀連結器的高度以影像測定器測定，由連接器端面測定0.5mm的位置以10mm間隔測定，以最大高度與最小高度的差特定之。 Further, the planar connector of the present invention suppresses deformation or bending and has excellent flatness. The flatness of the connector is that the connector is placed on a horizontal table, and the height of the planar connector is measured by an image measuring device. The position of the connector is measured at a position of 0.5 mm at an interval of 10 mm, with a maximum height and a minimum. The difference in height is specific.
此外，本發明的平面狀連結器，焊接強度及耐龜裂性優良。如上所述，成形品的焊接強度與耐龜裂性相關，根據本發明，可得焊接強度及耐龜裂性均良好的平面狀連結器。 Further, the planar connector of the present invention is excellent in welding strength and crack resistance. As described above, the weld strength of the molded article is related to the crack resistance, and according to the present invention, a planar connector having excellent weld strength and crack resistance can be obtained.
[實施例] [Examples]
以下，以實施例具體說明本發明，惟本發明不應限定於該等。 Hereinafter, the present invention will be specifically described by way of examples, but the invention should not be construed as limited thereto.
(液晶性聚合物的製造方法) (Method for producing liquid crystal polymer)
於具備攪拌機、回流管、單體投入口、氮氣導入口、減壓/流出管線之聚合容器，投入以下的原料單體、金屬觸媒，醯化劑，開始氮置換。 In a polymerization vessel equipped with a stirrer, a reflux pipe, a monomer inlet, a nitrogen gas inlet, and a pressure reduction/outflow line, the following raw material monomers, a metal catalyst, and a halogenating agent were introduced to start nitrogen substitution.
(I)4-羥基安息香酸：1041g(48莫耳%) (I) 4-hydroxybenzoic acid: 1041 g (48 mol%)
(II)2-羥基-6-萘甲酸：89g(3莫耳%) (II) 2-hydroxy-6-naphthoic acid: 89 g (3 mol%)
(III)對苯二甲酸：565g(21.7莫耳%) (III) Terephthalic acid: 565g (21.7 mol%)
(IV)間苯二甲酸：78g(3莫耳%) (IV) isophthalic acid: 78 g (3 mol%)
(V)4,4'-二羥基聯苯：711g(24.3莫耳%) (V) 4,4'-dihydroxybiphenyl: 711 g (24.3 mol%)
觸媒金屬(醋酸鉀觸媒)：110mg Catalytic metal (potassium acetate catalyst): 110mg
醯化劑(醋酸酐)：1645g Deuterated agent (acetic anhydride): 1645g
將原料放入聚合容器之後，使反應系的溫度上升到140℃，以140℃反應1小時。之後，進一步花5.5小時升溫至360℃，由此花30分鐘減壓至5Torr(即667Pa)，邊將醋酸、過剩的醋酸酐、其他的低沸分餾出，進行熔融聚合。攪拌扭力達到既定之值之後，導入氮氣由減壓狀態經過常壓呈加壓狀態，由聚合容器的下部排出聚合物，將膠條切割膠粒化。關於所得膠粒，於氮氣流下，以300℃進行8小時的熱處理。膠粒的熔點為358℃，結晶化熱為1.6J/g，熔融黏度為9Pa．s。 After the raw material was placed in the polymerization vessel, the temperature of the reaction system was raised to 140 ° C, and the reaction was carried out at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 360 ° C for 5.5 hours, and the pressure was reduced to 5 Torr (that is, 667 Pa) over 30 minutes, and acetic acid, excess acetic anhydride, and other low boiling fraction were distilled off to carry out melt polymerization. After the stirring torque reaches a predetermined value, the introduced nitrogen gas is pressurized under normal pressure through a reduced pressure state, and the polymer is discharged from the lower portion of the polymerization vessel to granulate the rubber strip. The obtained micelles were subjected to heat treatment at 300 ° C for 8 hours under a nitrogen stream. The melting point of the colloidal particles is 358 ° C, the heat of crystallization is 1.6 J / g, and the melt viscosity is 9 Pa. s.
再者，在於本實施例，熔融黏度的測定，係以如下條件進行。 Further, in the present embodiment, the measurement of the melt viscosity was carried out under the following conditions.
L=20mm、d=1mm的(股)東洋精密機械製毛細管流變儀1B型，以較液晶性聚合物的熔點高10~20℃的溫度，以剪斷速度1000/秒，遵照ISO11443，測定液晶性聚合物的熔融黏度。 L=20mm, d=1mm (share) Toyo Precision Machinery Capillary Rheometer Model 1B, measured at a temperature higher than the melting point of the liquid crystalline polymer by 10 to 20 ° C, at a shear rate of 1000 / sec, in accordance with ISO11443 The melt viscosity of the liquid crystalline polymer.
(液晶性聚合物以外的成分) (Components other than liquid crystal polymer)
使用雙軸擠出機，將上述所得之液晶性聚合物，與下述成分混合，得到複合樹脂組合物。各成分的調合量，係如第1表及第2表所示。 The liquid crystalline polymer obtained above was mixed with the following components using a twin-screw extruder to obtain a composite resin composition. The blending amount of each component is shown in Tables 1 and 2.
玻璃纖維：日本電氣玻璃(股)製ECS03T-786H，纖維徑10μm，長度3mm的切割膠條。 Glass fiber: ECS03T-786H made by Japan Electric Glass Co., Ltd., cutting tape with a fiber diameter of 10 μm and a length of 3 mm.
雲母：(股)YAMAGUCHI MICA製AB-25S，平均粒徑25μm Mica: (share) YAMAGUCHI MICA system AB-25S, average particle size 25μm
滑石：松村產業(股)製CROWN TALC PP，平均粒徑10μm Talc: CROWN TALC PP made by Matsumura Industry Co., Ltd., with an average particle size of 10 μm
基於下述方法，測定所得複合樹脂組合物或平面狀連結器的物性。將評估結果示於第1表及第2表。 The physical properties of the obtained composite resin composition or planar connector were measured by the following method. The results of the evaluation are shown in Tables 1 and 2.
(連結器平面度) (connector flatness)
將複合樹脂組合物，以第1圖所示形狀，全體的尺寸為39.82mm×39.82mm×1mmt，柵格部間距間隔為1.2mm的平面狀連結器(針孔數750針)，以下述成形條件射出成形。再者，閘門，係由柵格部的長度較長的邊使用薄膜閘門，閘門厚度為0.3mm。 The composite resin composition was formed into a planar connector having a size of 39.82 mm × 39.82 mm × 1 mmt and a grid portion pitch of 1.2 mm (the number of pinholes was 750 needles) in the shape shown in Fig. 1, and was formed as follows. Conditional injection molding. Further, the gate is a film gate which is made of a long side of the grid portion, and has a gate thickness of 0.3 mm.
[成形條件] [forming conditions]
成形機：住友重機械工業SE100DUZ Forming machine: Sumitomo Heavy Machinery Industry SE100DUZ
料管溫度：365℃-365℃-365℃-360℃ Tube temperature: 365 ° C - 365 ° C - 365 ° C - 360 ° C
金屬模具溫度：80℃ Metal mold temperature: 80 ° C
射出速度：200mm/sec Injection speed: 200mm/sec
保壓力：50MPa Pressure: 50MPa
保壓時間：1sec Holding time: 1sec
冷卻時間：5sec Cooling time: 5sec
螺桿旋轉數：120rpm Screw rotation number: 120rpm
螺桿背壓：2MPa Screw back pressure: 2MPa
將所得連結器靜置於水平的桌上，將連結器的高度以MITSUTOYO製QUICK VISION 404PROCNC影像測定器測定。此時，由連結器端面，將0.5mm的位置以10mm的間隔測定，特定最大高度與最小高度的差作為平面度。平面度之值越低表示連結器越平。 The obtained connector was placed on a horizontal table, and the height of the connector was measured by a QUICK VISION 404PROCNC image measuring instrument manufactured by MITSUTOYO. At this time, the position of 0.5 mm was measured at an interval of 10 mm from the end face of the connector, and the difference between the specific maximum height and the minimum height was defined as the flatness. The lower the value of the flatness, the flatter the connector.
(連結器最小填充壓力) (connector minimum filling pressure)
以365℃射出成形第1圖之平面狀連結器時，將可得良好的成形品的最小射出填充壓力作為最小填充壓力測定之。 When the planar connector of Fig. 1 was injection molded at 365 ° C, the minimum injection filling pressure of a obtainable molded article was measured as the minimum filling pressure.
(耐龜裂性) (crack resistance)
對第1圖的平面狀連結器，以下述條件進行IR回火，將柵格部以光學顯微鏡觀察，計測龜裂數。龜裂數越少，表示耐龜裂性越高。 The planar connector of Fig. 1 was subjected to IR tempering under the following conditions, and the grid portion was observed with an optical microscope to measure the number of cracks. The smaller the number of cracks, the higher the crack resistance.
[IR回火條件] [IR tempering conditions]
測定機：日本PULSE技術研究所製之大型桌上回焊裝置RF-300(使用遠紅外線加熱器) Measuring machine: Large table reflow device RF-300 manufactured by Japan PULSE Technology Research Institute (using far infrared heater)
試料輸送速度：140mm/sec Sample conveying speed: 140mm/sec
回火爐穿過時間：5min Backfire furnace crossing time: 5min
溫度條件： Temperature conditions:
預熱區：150℃ Preheating zone: 150 ° C
回火區：240℃ Tempering area: 240 ° C
波峰溫度：260℃ Peak temperature: 260 ° C
(焊接強度) (welding strength)
將複合樹脂組合物，以下述成形條件射出成形為測定用試驗片(125mm×13mm×0.4mm，2點薄膜閘門)。將所得試驗片的焊接強度，以下述測定條件測定。 The composite resin composition was injection-molded into a test piece for measurement (125 mm × 13 mm × 0.4 mm, two-point film shutter) under the following molding conditions. The weld strength of the obtained test piece was measured under the following measurement conditions.
[成形條件] [forming conditions]
成形機：住友重機械工業SE100DU Forming machine: Sumitomo Heavy Machinery Industry SE100DU
料管溫度：365℃-365℃-365℃-365℃-365℃-365℃ Tube temperature: 365 ° C - 365 ° C - 365 ° C - 365 ° C - 365 ° C - 365 ° C
金屬模具溫度：90℃ Metal mold temperature: 90 ° C
射出速度：200mm/sec Injection speed: 200mm/sec
保壓力：70MPa Pressure: 70MPa
保壓時間：5sec Holding time: 5sec
冷卻時間：8sec Cooling time: 8sec
螺桿旋轉數：150rpm Screw rotation number: 150rpm
螺桿背壓：1MPa Screw back pressure: 1MPa
[測定條件] [Measurement conditions]
測定機：ORIENTEC公司製TENSILON萬能試驗機RTM-100 Measuring machine: TENSILON universal testing machine RTM-100 made by ORIENTEC
荷重元：100kg Load weight: 100kg
金屬模具溫度：90℃ Metal mold temperature: 90 ° C
夾具間距離：2.5mm Distance between fixtures: 2.5mm
夾力：2.0kgf/cm2 Clamping force: 2.0kgf/cm 2
拉張速度：0.5mm/min Pulling speed: 0.5mm/min
(荷重彎曲溫度) (load bending temperature)
將複合樹脂組合物，以下述成形條件射出成形為測定用試驗片(複合樹脂組合物4mm×10mm×80mm)。將所得試驗片之荷 重彎曲溫度，遵照ISO75-1,2測定。 The composite resin composition was injection-molded into a test piece for measurement (composite resin composition: 4 mm × 10 mm × 80 mm) under the following molding conditions. The resulting test piece Heavy bending temperature, measured in accordance with ISO 75-1, 2.
[成形條件] [forming conditions]
成形機：住友重機械工業SE100DU Forming machine: Sumitomo Heavy Machinery Industry SE100DU
料管溫度：360℃-370℃-370℃-360℃-340℃-330℃ Tube temperature: 360°C-370°C-370°C-360°C-340°C-330°C
金屬模具溫度：80℃ Metal mold temperature: 80 ° C
射出速度：33mm/sec Injection speed: 33mm/sec
保壓力：50MPa Pressure: 50MPa
保壓時間：2sec Holding time: 2sec
冷卻時間：10sec Cooling time: 10sec
螺管旋轉數：120rpm Number of solenoid rotations: 120rpm
如第1及2表所示，本發明之平面狀平面狀連結器，在於平面度、耐龜裂性及焊接強度均優良。在於比較例8及9的平面狀連結器的耐龜裂性及焊接強度，雖然與本發明相同，但是平面度低。根據本發明，可得平面度、耐龜裂性及焊接強度均良好的平面狀連結器。 As shown in the first and second tables, the planar planar connector of the present invention is excellent in flatness, crack resistance, and weld strength. The crack resistance and the welding strength of the planar connectors of Comparative Examples 8 and 9 were the same as those of the present invention, but the flatness was low. According to the present invention, a planar connector having good flatness, crack resistance and weld strength can be obtained.
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| CN105837805A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| JP6774329B2 (en) * | 2016-12-28 | 2020-10-21 | 住友化学株式会社 | Liquid crystal polyester resin composition |
| KR102085262B1 (en) * | 2017-05-10 | 2020-03-05 | 포리프라스틱 가부시키가이샤 | Wholly aromatic polyester and polyester resin composition |
| WO2023145517A1 (en) * | 2022-01-26 | 2023-08-03 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for planar connector, and planar connector obtained using same |
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| JP2003268252A (en) * | 2002-03-19 | 2003-09-25 | Polyplastics Co | Liquid crystalline polymer composition |
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| JP5165492B2 (en) * | 2008-05-23 | 2013-03-21 | ポリプラスチックス株式会社 | Planar connector |
| JP5308800B2 (en) * | 2008-12-09 | 2013-10-09 | Ｊｘ日鉱日石エネルギー株式会社 | Liquid crystalline polyester resin composition |
| TWI586750B (en) * | 2011-02-28 | 2017-06-11 | 住友化學股份有限公司 | Liquid crystal polyester composition and process for producing the same |
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| JP5136720B2 (en) * | 2011-04-06 | 2013-02-06 | 東レ株式会社 | Liquid crystalline polyester resin composition and metal composite molded article using the same |
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